Tetrafluoropropene compositions and uses thereof

ABSTRACT

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a tetrafluoropropene and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/362,354, filed Nov. 28, 2016, now U.S. Pat. No. 10,208,236, which isa divisional of U.S. patent application Ser. No. 14/499,454, filed Sep.29, 2014, issued as U.S. Pat. No. 9,540,556, which is a divisional ofU.S. patent application Ser. No. 13/858,182, filed Apr. 8, 2013,abandoned, which is a divisional of U.S. patent application Ser. No.12/618,890, filed Nov. 16, 2009, abandoned, which claims the prioritybenefit of U.S. Provisional Patent Application No. 61/116,029, filedNov. 19, 2008, and U.S. Provisional Patent Application No. 61/180,281,filed May 21, 2009.

BACKGROUND 1. Field of the Disclosure

The present disclosure relates to compositions for use in refrigeration,air-conditioning, and heat pump systems wherein the compositioncomprises a tetrafluoropropene and at least one other compound. Thecompositions of the present invention are useful in processes forproducing cooling or heat, as heat transfer fluids, foam blowing agents,aerosol propellants, and fire suppression and fire extinguishing agents.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase outof certain HFC refrigerants. Currently, the automobile industry isfacing regulations relating to global warming potential for refrigerantsused in mobile air-conditioning. Therefore, there is a great currentneed to identify new refrigerants with reduced global warming potentialfor the mobile air-conditioning market. Should the regulations be morebroadly applied in the future, for instance for stationary airconditioning and refrigeration systems, an even greater need will befelt for refrigerants that can be used in all areas of the refrigerationand air-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂. Many of these suggested replacements aretoxic, flammable, and/or have low energy efficiency. New replacementsare also being proposed for HCFC-22, R404A, R407C, and R410A amongothers. Therefore, new alternative refrigerants are being sought.

BRIEF SUMMARY

The object of the present disclosure is to provide novel refrigerantcompositions and heat transfer fluid compositions that provide uniquecharacteristics to meet the demands of low or zero ozone depletionpotential and lower global warming potential as compared to currentrefrigerants.

Disclosed are compositions selected from the group consisting ofcompositions comprising:

-   -   HFO-1234yf, HFC-152a, and HFC-134a;    -   HFO-1234yf, HFC-125, and HFC-152a;    -   HFO-1234yf, HFC-125, and HFC-134a;    -   HFO-1234yf, HFC-32, and HFC-134a;    -   HFO-1234yf, HFC-32, HFC-125, and HFC-134a;    -   HFO-1234ze and HFC-32;    -   HFO-1234ze and HFC-125;    -   HFO-1234ze, HFC-125, and HFC-152a;    -   HFO-1234ze, HFC-125, and HFC-134a;    -   HFO-1234ze, HFC-32, and HFC-134a;    -   and    -   HFO-1234ze, HFC-32, HFC-125, and HFC-134a.

Also disclosed are non-flammable compositions comprising no more thanabout 60 weight percent HFO-1234yf and at least about 40 weight percentHFC-134a.

Also disclosed are compositions comprising at least about 85 weightpercent HFO-1234yf and up to about 15 weight percent HFC-32.

DETAILED DESCRIPTION

Before addressing details of embodiments described below, some terms aredefined or clarified.

Definitions

As used herein, the term heat transfer composition means a compositionused to carry heat from a heat source to a heat sink.

A heat source is defined as any space, location, object or body fromwhich it is desirable to add, transfer, move or remove heat. Examples ofheat sources is spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, industrial water chillers orthe passenger compartment of an automobile requiring air-conditioning.In some embodiments, the heat transfer composition may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). In other embodiments, evaporative cooling processes mayutilize heat transfer compositions as well.

A heat sink is defined as any space, location, object or body capable ofabsorbing heat. A vapor compression refrigeration system is one exampleof such a heat sink.

A heat transfer system is the system (or apparatus) used to produce aheating or cooling effect in a particular space. A heat transfer systemmay be a mobile system or a stationary system.

Examples of heat transfer systems included but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,mobile refrigerators, mobile air conditioning units, dehumidifiers, andcombinations thereof.

As used herein, mobile heat transfer system refers to any refrigeration,air conditioner, or heating apparatus incorporated into a transportationunit for the road, rail, sea or air. In addition, mobile refrigerationor air conditioner units, include those apparatus that are independentof any moving carrier and are known as “intermodal” systems. Suchintermodal systems include “container’ (combined sea/land transport) aswell as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps (including but not limited to chillers, hightemperature heat pumps, residential, commercial or industrial airconditioning systems, and including window, ductless, ducted, packagedterminal, chillers, and those exterior but connected to the buildingsuch as rooftop systems). In stationary refrigeration applications, thedisclosed compositions may be useful in equipment including commercial,industrial or residential refrigerators and freezers, ice machines,self-contained coolers and freezers, flooded evaporator chillers, directexpansion chillers, walk-in and reach-in coolers and freezers, andcombination systems. In some embodiments, the disclosed compositions maybe used in supermarket refrigeration systems. Additionally, stationaryapplications may utilize a secondary loop system that uses a primaryrefrigerant to produce cooling in one location that is transferred to aremote location via a secondary heat transfer fluid.

Refrigeration capacity (sometimes referred to as cooling capacity) is aterm to define the change in enthalpy of a refrigerant in an evaporatorper pound of refrigerant circulated, i.e., the heat removed by therefrigerant in the evaporator per a given time. The refrigerationcapacity is a measure of the ability of a refrigerant or heat transfercomposition to produce cooling. Therefore, the higher the capacity thegreater the cooling that is produced.

Coefficient of performance (COP) is the amount of heat removed dividedby the required energy input to operate the cycle. The higher the COP,the higher is the energy efficiency. COP is directly related to theenergy efficiency ratio (EER) that is the efficiency rating forrefrigeration or air conditioning equipment at a specific set ofinternal and external temperatures.

The term “subcooling” is meant the reduction of the temperature of aliquid below that liquid's saturation point for a given pressure. Thesaturation point is the temperature at which the vapor is completelycondensed to a liquid, but subcooling (continues to cool the liquid to alower temperature liquid at the given pressure. By cooling a liquidbelow the saturation temperature (or bubble point temperature), the netrefrigeration capacity can be increased. Subcooling thereby improvesrefrigeration capacity and energy efficiency of a system. Subcool amountis the amount of cooling below the saturation temperature (in degrees).

Superheat is a term that defines how far above its saturation vaportemperature (the temperature at which, if the composition is cooled, thefirst drop of liquid is formed, also referred to as the “dew point”) avapor composition is heated.

Temperature glide (sometimes referred to simply as “glide”) is theabsolute value of the difference between the starting and endingtemperatures of a phase-change process by a refrigerant within acomponent of a refrigerant system, exclusive of any subcooling orsuperheating. This term may be used to describe condensation orevaporation of a near azeotropic or non-azeotropic composition.

By azeotropic composition is meant a constant-boiling mixture of two ormore substances that behave as a single substance. One way tocharacterize an azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has the samecomposition as the liquid from which it is evaporated or distilled,i.e., the mixture distills/refluxes without compositional change.Constant-boiling compositions are characterized as azeotropic becausethey exhibit either a maximum or minimum boiling point, as compared withthat of the non-azeotropic mixture of the same compounds. An azeotropiccomposition will not fractionate within a refrigeration or airconditioning system during operation. Additionally, an azeotropiccomposition will not fractionate upon leakage from a refrigeration orair conditioning system.

A near-azeotropic composition (also commonly referred to as an“azeotrope-like composition”) is a substantially constant boiling liquidadmixture of two or more substances that behaves essentially as a singlesubstance. One way to characterize a near-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas substantially the same composition as the liquid from which it wasevaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition isnear-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isless than about 10 percent.

A non-azeotropic composition is a mixture of two or more substances thatbehaves as a simple mixture rather than a single substance. One way tocharacterize a non-azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has a substantiallydifferent composition as the liquid from which it was evaporated ordistilled, that is, the admixture distills/refluxes with substantialcomposition change. Another way to characterize a non-azeotropiccomposition is that the bubble point vapor pressure and the dew pointvapor pressure of the composition at a particular temperature aresubstantially different. Herein, a composition is non-azeotropic if,after 50 weight percent of the composition is removed, such as byevaporation or boiling off, the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed is greater thanabout 10 percent.

As used herein, the term “lubricant” means any material added to acomposition or a compressor (and in contact with any heat transfercomposition in use within any heat transfer system) that provideslubrication to the compressor to aid in preventing parts from seizing.

As used herein, compatibilizers are compounds which improve solubilityof the hydrofluorocarbon of the disclosed compositions in heat transfersystem lubricants. In some embodiments, the compatibilizers improve oilreturn to the compressor. In some embodiments, the composition is usedwith a system lubricant to reduce oil-rich phase viscosity.

As used herein, oil-return refers to the ability of a heat transfercomposition to carry lubricant through a heat transfer system and returnit to the compressor. That is, in use, it is not uncommon for someportion of the compressor lubricant to be carried away by the heattransfer composition from the compressor into the other portions of thesystem. In such systems, if the lubricant is not efficiently returned tothe compressor, the compressor will eventually fail due to lack oflubrication.

As used herein, “ultra-violet” dye is defined as a UV fluorescent orphosphorescent composition that absorbs light in the ultra-violet or“near” ultra-violet region of the electromagnetic spectrum. Thefluorescence produced by the UV fluorescent dye under illumination by aUV light that emits at least some radiation with a wavelength in therange of from 10 nanometers to about 775 nanometers may be detected.

Flammability is a term used to mean the ability of a composition toignite and/or propagate a flame. For refrigerants and other heattransfer compositions, the lower flammability limit (“LFL”) is theminimum concentration of the heat transfer composition in air that iscapable of propagating a flame through a homogeneous mixture of thecomposition and air under test conditions specified in ASTM (AmericanSociety of Testing and Materials) E681. The upper flammability limit(“UFL”) is the maximum concentration of the heat transfer composition inair that is capable of propagating a flame through a homogeneous mixtureof the composition and air under the same test conditions. Theflammability test, ASTM E681, is run on the liquid phase and the vaporphase present in a closed container above the liquid at specifiedtemperatures as designated by ASHRAE (American Society of Heating,Refrigerating and Air-Conditioning Engineers) in the ASHRAE Standard 34.In order to be classified by ASHRAE as non-flammable, a refrigerant mustbe non-flammable under the conditions of ASTM E681 as formulated in boththe liquid and vapor phase as well as during leakage scenarios.

Global warming potential (GWP) is an index for estimating relativeglobal warming contribution due to atmospheric emission of a kilogram ofa particular greenhouse gas compared to emission of a kilogram of carbondioxide. GWP can be calculated for different time horizons showing theeffect of atmospheric lifetime for a given gas. The GWP for the 100 yeartime horizon is commonly the value referenced. For mixtures, a weightedaverage can be calculated based on the individual GWPs for eachcomponent.

Ozone depletion potential (ODP) is a number that refers to the amount ofozone depletion caused by a substance. The ODP is the ratio of theimpact on ozone of a chemical compared to the impact of a similar massof CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is definedto be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0.HFCs have zero ODP because they do not contain chlorine.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a composition,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition, process,method, article, or apparatus. Further, unless expressly stated to thecontrary, “or” refers to an inclusive or and not to an exclusive or. Forexample, a condition A or B is satisfied by any one of the following: Ais true (or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed provided that these additional included materials, steps,features, components, or elements do materially affect the basic andnovel characteristic(s) of the claimed invention. The term ‘consistingessentially of’ occupies a middle ground between “comprising” and‘consisting of’.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the disclosed compositions,suitable methods and materials are described below. All publications,patent applications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

Compositions

Disclosed are compositions comprising tetrafluoropropene and at leastone other compound. Tetrafluoropropene may be either1,3,3,3-tetrafluoropropene (HFO-1234ze) or 2,3,3,3-tetrafluoropropene(HFO-1234yf). HFO-1234ze may exist as different configurational isomers,E- (trans-) or Z- (cis-), or stereoisomers. The present invention isintended to include all single configurational isomers, singlestereoisomers or any combination or mixture thereof.

Both HFO-1234ze and HFO-1234yf may be made by methods known in the art.

The disclosed compositions also contain other fluorinated compoundsselected from the group consisting of difluoromethane (HFC-32),tetrafluoroethane, pentafluoroethane (HFC-125), and difluoroethane(1,1-difluoroethane or HFC-152a). Tetrafluoroethane may be1,1,1,2-tetrafluoroethane (HFC-134a) or 1,1,2,2-tetrafluoroethane(HFC-134). These fluorinated compounds are commercially available or maybe made by methods known in the art.

In one embodiment, compositions are disclosed comprising:

HFO-1234yf and HFC-32;

HFO-1234yf and HFC-134a;

HFO-1234yf, HFC-152a, and HFC-134a;

HFO-1234yf, HFC-125, and HFC-152a;

HFO-1234yf, HFC-125, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-125;

HFO-1234yf, HFC-32, HFC-125, and HFC-134a;

HFO-1234ze and HFC-32;

HFO-1234ze and HFC-125;

HFO-1234ze, HFC-125, and HFC-152a;

HFO-1234ze, HFC-125, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-125; and

HFO-1234ze, HFC-32, HFC-125, and HFC-134a.

In another embodiment, compositions are disclosed consisting essentiallyof:

HFO-1234yf and HFC-32;

HFO-1234yf and HFC-134a;

HFO-1234yf, HFC-152a, and HFC-134a;

HFO-1234yf, HFC-125, and HFC-152a;

HFO-1234yf, HFC-125, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-125;

HFO-1234yf, HFC-32, HFC-125, and HFC-134a;

HFO-1234ze and HFC-32;

HFO-1234ze and HFC-125;

HFO-1234ze, HFC-125, and HFC-152a;

HFO-1234ze, HFC-125, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-125; and

HFO-1234ze, HFC-32, HFC-125, and HFC-134a.

In one embodiment, any of the disclosed compositions may be generallyuseful when the tetrafluoropropene is present at about 1 weight percentto about 99 weight percent of the overall composition. In anotherembodiment, the useful compositions comprise about 20 weight percent toabout 99 weight percent tetrafluoropropene. In another embodiment, theuseful compositions comprise about 40 weight percent to about 99 weightpercent tetrafluoropropene. And in yet another embodiment, the usefulcompositions comprise about 50 weight percent to about 99 weight percenttetrafluoropropene.

For ternary compositions as described herein, in one embodiment, thecompositions may comprise from about 1 weight percent to about 98 weightpercent tetrafluoropropene. In another embodiment, the compositionscomprise from about 20 weight percent to about 98 weight percenttetrafluoropropene. In another embodiment, the compositions comprisefrom about 40 weight percent to about 98 weight percenttetrafluoropropene. And in yet another embodiment, the compositionscomprise from about 50 weight percent to about 98 weight percenttetrafluoropropene. In certain embodiments, the disclosed compositionscomprising trans-HFO-1234ze and HFC-125 contain from about 80 weightpercent to about 99 weight percent trans-HFO-1234ze and from about 20weight percent to about 1 weight percent HFC-125. In other embodiments,the compositions comprise from about 85 weight percent to about 95weight percent HFO-1234ze and from about 15 weight percent to about 5weight percent HFC-125.

In some embodiment, the disclosed compositions comprisingtrans-HFO-1234ze and HFC-32 contain from about 20 weight percent toabout 90 weight percent trans-HFO-1234ze and from about 80 weightpercent to about 10 weight percent HFC-32.

In one embodiment, the disclosed compositions are generally expected tomaintain the desired properties and functionality when the componentsare present in the concentrations as listed +/−2 weight percent.

In some embodiments, the disclosed compositions are found to benear-azeotropic. Near-azeotropic compositions comprisingtetrafluoropropene have been identified at the specified temperature aslisted in Table 1.

TABLE 1 Near-azeotrope range Temp Components (weight percent) (° C.)HFO-1234yf/HFC-152a/HFC-134a 1-98/1-98/1-98 23 HFO-1234yf/152a/1251-98/1-98/1-98 23 HFO-1234yf/HFC-125/HFC-134a 1-98/1-98/1-98 23HFO-1234yf/HFC-32/HFC-134a 1-98/1-4/1-98 and 23 1-55/45-98/1-55HFO-1234yf/HFC-134a/HFC-125/HFC-32 1-97/1-97/1-97/1-5, 231-35/1-40/30-78/6-39, and 1-50/1-40/1-50/40-97

Certain of the compositions of the present invention are non-azeotropiccompositions. A non-azeotropic composition may have certain advantagesover azeotropic or near azeotropic mixtures. The temperature glide of anon-azeotropic composition provides an advantage in counter current flowheat exchanger arrangements.

In some embodiments, the disclosed compositions are non-flammable asdetermined using ASTM (American Society of Testing and Materials)E681-2004, the standard test for measuring flammability of refrigerants.

In one embodiment, the composition is a non-flammable compositioncomprising no more than about 60 weight percent HFO-1234yf and at leastabout 40 weight percent HFC-134a at about 60° C.

In another embodiment, the composition is a non-flammable compositioncomprising no more than about 53 weight percent HFO-1234yf and at leastabout 47 weight percent HFC-134a at about 100° C.

In one embodiment, a refrigerant mixture with some temperature glide maybe acceptable in the industry or even have advantages as mentionedpreviously herein. R407C is an example of a commercial refrigerantproduct with glide. It has been demonstrated that certain compositionsas disclosed herein provide a refrigerant composition with temperatureglide that approaches the temperature glide of R407C.

In one embodiment, the compositions comprise at least about 85 weightpercent HFO-1234yf and up to about 15 weight percent HFC-32. Suchcompositions have been demonstrated to have minimal temperature glideand maintain cooling capacity and energy efficiency at a similar levelto R407C. In another embodiment, the compositions comprise at leastabout 90 weight percent HFO-1234yf and up to about 10 weight percentHFC-32. In another embodiment, the compositions comprise at least about95 weight percent HFO-1234yf and up to about 5 weight percent HFC-32.

In some embodiments, in addition to the tetrafluoropropene andfluorinated compounds, the disclosed compositions may comprise optionalother components.

In some embodiments, the optional other components (also referred toherein as additives) in the compositions disclosed herein may compriseone or more components selected from the group consisting of lubricants,dyes, solubilizing agents, compatibilizers, stabilizers, tracers,perfluoropolyethers, anti wear agents, extreme pressure agents,corrosion and oxidation inhibitors, metal surface energy reducers, metalsurface deactivators, free radical scavengers, foam control agents,viscosity index improvers, pour point depressants, detergents, viscosityadjusters, and mixtures thereof. Indeed, many of these optional othercomponents fit into one or more of these categories and may havequalities that lend themselves to achieve one or more performancecharacteristic.

In some embodiments, one or more additive is present in the compositionsdisclosed in small amounts relative to the overall composition. In someembodiments, the amount of additive(s) concentration in the disclosedcompositions is from less than about 0.1 weight percent to as much asabout 5 weight percent of total additive. In some the additives arepresent in the disclosed compositions in an amount between about 0.1weight percent to about 3.5 weight percent. The additive component(s)selected for the disclosed composition is selected on the basis of theutility and/or individual equipment components or the systemrequirements.

In some embodiments, the disclosed compositions include at least onelubricant selected from the group consisting of mineral oils (oils ofmineral origin), synthetic lubricants, and mixtures thereof.

In some embodiment, the disclosed compositions further comprise at leastone lubricant selected from the group consisting of mineral oils,alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly alphaolefins, polyalkylene glycols, dibasic acid esters, polyesters,neopentyl esters, polyvinyl ethers, silicones, silicate esters,fluorinated compounds, phosphate esters and mixtures thereof.

In some embodiments, the disclosed compositions include at least onelubricant selected from those suitable for use with refrigeration orair-conditioning equipment. In some embodiments, the disclosedcompositions include at least one synthetic oil selected from thosereadily known in the field of compression refrigeration lubrication.

In some embodiments, at least one optional component is a mineral oillubricant. In some embodiments, the mineral oil lubricant is selectedfrom the group consisting of paraffins (including straight carbon chainsaturated hydrocarbons, branched carbon chain saturated hydrocarbons,and mixtures thereof), naphthenes (including saturated cyclic and ringstructures), aromatics (those with unsaturated hydrocarbons containingone or more ring, wherein one or more ring is characterized byalternating carbon-carbon double bonds) and non-hydrocarbons (thosemolecules containing atoms such as sulfur, nitrogen, oxygen and mixturesthereof), and mixtures and combinations of thereof.

Some embodiments may contain one or more synthetic lubricant. In someembodiments, the synthetic lubricant is selected from the groupconsisting of alkyl substituted aromatics (such as benzene ornaphthalene substituted with linear, branched, or mixtures of linear andbranched alkyl groups, often generically referred to as alkylbenzenes),synthetic paraffins and naphthenes, poly (alpha olefins), polyglycols(including polyalkylene glycols), dibasic acid esters, polyesters,neopentyl esters, polyvinyl ethers (PVEs), silicones, silicate esters,fluorinated compounds, phosphate esters and mixtures and combinationsthereof.

In some embodiments, the compositions disclosed herein contain at leastone commercially available lubricant. In some embodiments thecompositions disclosed herein contain at least one lubricant selectedfrom the group consisting of BVM 100 N (paraffinic mineral oil sold byBVA Oils), Suniso® 1GS, Suniso® 3GS and Suniso® 5GS (naphthenic mineraloils sold by Crompton Co.), Sontex® 372LT (naphthenic mineral oil soldby Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by CalumetLubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenessold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold byNippon Oil), polyol esters (POEs) such as Castrol® 100 (Castrol, UnitedKingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (DowChemical, Midland, Mich.), and mixtures thereof.

In other embodiments, at least one of the lubricants further includethose lubricants that have been designed for use with hydrofluorocarbonrefrigerants and are miscible with compositions as disclosed hereinunder compression refrigeration and air-conditioning apparatus'operating conditions. In some embodiments, the lubricants are selectedby considering a given compressor's requirements and the environment towhich the lubricant will be exposed.

In some embodiments, the lubricant is present in an amount of less than5.0 weight percent to the total composition. In other embodiments, theamount of lubricant is between about 0.1 and 3.5 weight percent of thetotal composition.

Notwithstanding the above weight ratios for compositions disclosedherein, it is understood that in some heat transfer systems, while thecomposition is being used, it may acquire additional lubricant from oneor more equipment component of such heat transfer system. For example,in some refrigeration, air conditioning and heat pump systems,lubricants may be charged in the compressor and/or the compressorlubricant sump. Such lubricant would be in addition to any lubricantadditive present in the refrigerant in such a system. In use, therefrigerant composition when in the compressor may pick up an amount ofthe equipment lubricant to change the refrigerant-lubricant compositionfrom the starting ratio.

In such heat transfer systems, even when the majority of the lubricantresides within the compressor portion of the system, the entire systemmay contain a total composition with as much as about 75 weight percentto as little as about 1.0 weight percent of the composition beinglubricant. In one embodiment, in some systems, for example supermarketrefrigerated display cases, the system may contain about 3 weightpercent lubricant (over and above any lubricant present in therefrigerant composition prior to charging the system) and 97 weightpercent refrigerant. In another embodiment, in some systems, for examplemobile air conditioning systems, the system may contain about 20 weightpercent lubricant (over and above any lubricant present in therefrigerant composition prior to charging the system) and about 80weight percent refrigerant.

In some embodiments, the disclosed compositions include at least onedye. In some embodiments, the disclosed compositions include at leastone ultra-violet (UV) dye.

In some embodiments, the disclosed compositions include at least one UVdye that is a fluorescent dye. In some embodiments, the describedcompositions include at least one UV dye that is a fluorescent dyeselected from the group consisting of naphthalimides, perylenes,coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, and derivatives of said dye andcombinations thereof.

In some embodiments, the disclosed compositions contain from about 0.001weight percent to about 1.0 weight percent UV dye. In other embodiments,the UV dye is present in an amount of from about 0.005 weight percent toabout 0.5 weight percent; and in other embodiments, the UV dye ispresent in an amount of from 0.01 weight percent to about 0.25 weightpercent of the total composition.

In some embodiments, the UV dye is a useful component for detectingleaks of the composition by permitting one to observe the fluorescenceof the dye at or in the vicinity of a leak point in an apparatus (e.g.,refrigeration unit, air-conditioner or heat pump). One may observe theUV emission, e.g., fluorescence from the dye under an ultra-violetlight. Therefore, if a composition containing such a UV dye is leakingfrom a given point in an apparatus, the fluorescence can be detected atthe leak point, or in the vicinity of the leak point.

In some embodiments, the described compositions further contain at leastone solubilizing agent selected to improve the solubility of one or moredye in the disclosed compositions. In some embodiments, the weight ratioof dye to solubilizing agent ranges from about 99:1 to about 1:1.

In some embodiments, solubilizing agents in the disclosed compositionsinclude at least one compound selected from the group consisting ofhydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such asdipropylene glycol dimethyl ether), amides, nitriles, ketones,chlorocarbons (such as methylene chloride, trichloroethylene,chloroform, or mixtures thereof), esters, lactones, aromatic ethers,fluoroethers and 1,1,1-trifluoroalkanes and mixtures thereof.

In some embodiments, at least one compatibilizer is selected to improvethe compatibility of one or more lubricant with the disclosedcompositions. In some embodiments, the compatibilizer is selected fromthe group consisting of hydrocarbons, hydrocarbon ethers,polyoxyalkylene glycol ethers (such as dipropylene glycol dimethylether), amides, nitriles, ketones, chlorocarbons (such as methylenechloride, trichloroethylene, chloroform, or mixtures thereof), esters,lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, andmixtures thereof.

In some embodiments, one or more solubilizing agent and/orcompatibilizer is selected from the group consisting of hydrocarbonethers consisting of the ethers containing only carbon, hydrogen andoxygen, such as dimethyl ether (DME) and mixtures thereof.

In some embodiments, the disclosed composition includes at least onelinear or cyclic aliphatic or aromatic hydrocarbon compatibilizercontaining from 5 to 15 carbon atoms. In some embodiments, thecompatibilizer is selected from the group consisting of at least onehydrocarbon; in other embodiments, the compatibilizer is a hydrocarbonselected from the group consisting of at least pentane, hexane, octane,nonane, decane, commercially available from Exxon Chemical (USA) underthe trademarks Isopar® H (a high purity C₁₁ to C₁₂ iso-paraffinic),Aromatic 150 (a C₉ to C₁₁ aromatic), Aromatic 200 (a C₉ to C₁₅ aromatic)and Naptha 140 and mixtures thereof.

In some embodiments, the disclosed compositions include at least onepolymeric compatibilizer. In some embodiments, the disclosedcompositions include at least one a polymeric compatibilizer selectedfrom those that are random copolymers of fluorinated and non-fluorinatedacrylates, wherein the polymer comprises repeating units of at least onemonomer represented by the formulae CH₂═C(R¹)CO₂R², CH₂═C(R³)C₆H₄R⁴, andCH₂═C(R⁵)C₆H₄XR⁶, wherein X is oxygen or sulfur; R¹, R³, and R⁵ areindependently selected from the group consisting of H and C₁-C₄ alkylradicals; and R², R⁴, and R⁶ are independently selected from the groupconsisting of carbon-chain-based radicals containing C, and F, and mayfurther contain H, Cl, ether oxygen, or sulfur in the form of thioether,sulfoxide, or sulfone groups and mixtures thereof. Examples of suchpolymeric compatibilizers include those commercially available from E.I. du Pont de Nemours & Co. (Wilmington, Del., 19898, USA) under thetrademark Zonyl® PHS. Zonyl® PHS is a random copolymer made bypolymerizing 40 weight percent CH₂═C(CH₃)CO₂CH₂CH₂(CF₂CF₂)_(m)F (alsoreferred to as Zonyl® fluoromethacrylate or ZFM) wherein m is from 1 to12, primarily 2 to 8, and 60 weight percent lauryl methacrylate(CH₂═C(CH₃)CO₂(CH₂)₁₁CH₃, also referred to as LMA).

In some embodiments, the compatibilizer component contains from about0.01 to 30 weight percent (based on total amount of compatibilizer) ofan additive which reduces the surface energy of metallic copper,aluminum, steel, or other metals and metal alloys thereof found in heatexchangers in a way that reduces the adhesion of lubricants to themetal. Examples of metal surface energy reducing additives include thosecommercially available from DuPont under the trademarks Zonyl® FSA,Zonyl® FSP, and Zonyl® FSJ.

In some embodiments, the disclosed compositions further include metalsurface deactivators. In some embodiments, at least one metal surfacedeactivator is selected from the group consisting of areoxalyl bis(benzylidene) hydrazide (CAS reg no. 6629-10-3),N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no.32687-78-8),2,2,′-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CASreg no. 70331-94-1), N,N′-(disalicyclidene)-1,2-diaminopropane (CAS regno. 94-91-7) and ethylenediaminetetra-acetic acid (CAS reg no. 60-00-4)and its salts, and mixtures thereof.

In some embodiments, the compositions disclosed herein further includeat least one stabilizer selected from the group consisting of hinderedphenols, thiophosphates, butylated triphenylphosphorothionates, organophosphates, or phosphites, aryl alkyl ethers, terpenes, terpenoids,epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols,lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalic acid, diphenylterephthalic acid, ionic liquids, and mixtures thereof.

In some embodiments, said at least one stabilizer is selected from thegroup consisting of tocopherol; hydroquinone; t-butyl hydroquinone;monothiophosphates; and dithiophosphates, commercially available fromCiba Specialty Chemicals, Basel, Switzerland, hereinafter “Ciba”, underthe trademark Irgalube® 63; dialkylthiophosphate esters, commerciallyavailable from Ciba under the trademarks Irgalube® 353 and Irgalube®350, respectively; butylated triphenylphosphorothionates, commerciallyavailable from Ciba under the trademark Irgalube® 232; amine phosphates,commercially available from Ciba under the trademark Irgalube® 349(Ciba); hindered phosphites, commercially available from Ciba asIrgafos® 168 and Tris-(di-tert-butylphenyl)phosphite, commerciallyavailable from Ciba under the trademark Irgafos® OPH; (Di-n-octylphosphite); and iso-decyl diphenyl phosphite, commercially availablefrom Ciba under the trademark Irgafos® DDPP; trialkyl phosphates, suchas trimethyl phosphate, triethylphosphate, tributyl phosphate, trioctylphosphate, and tri(2-ethylhexyl)phosphate; triaryl phosphates includingtriphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate; andmixed alkyl-aryl phosphates including isopropylphenyl phosphate (IPPP),and bis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenylphosphates, such as those commercially available under the trademarkSyn-O-Ad® including Syn-O-Ad® 8784; tert-butylated triphenyl phosphatessuch as those commercially available under the trademark Durad®620;isopropylated triphenyl phosphates such as those commercially availableunder the trademarks Durad® 220 and Durad®110; anisole;1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene;myrcene, alloocimene, limonene (in particular, d-limonene); retinal;pinene; menthol; geraniol; farnesol; phytol; Vitamin A; terpinene;delta-3-carene; terpinolene; phellandrene; fenchene; dipentene;caratenoids, such as lycopene, beta carotene, and xanthophylls, such aszeaxanthin; retinoids, such as hepaxanthin and isotretinoin; bornane;1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether;trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane;3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd); ascorbic acid; methanethiol (methyl mercaptan);ethanethiol (ethyl mercaptan); Coenzyme A; dimercaptosuccinic acid(DMSA); grapefruit mercaptan((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide(1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially available fromCiba under the trademark Irganox® HP-136; benzyl phenyl sulfide;diphenyl sulfide; diisopropylamine; dioctadecyl 3,3′-thiodipropionate,commercially available from Ciba under the trademark Irganox® PS 802(Ciba); didodecyl 3,3′-thiopropionate, commercially available from Cibaunder the trademark Irganox® PS 800;di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, commercially availablefrom Ciba under the trademark Tinuvin® 770;poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate,commercially available from Ciba under the trademark Tinuvin® 622LD(Ciba); methyl bis tallow amine; bis tallow amine;phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane (DMAMS);tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane;vinyltrimethoxysilane; 2,5-difluorobenzophenone;2′,5′-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone;benzyl phenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionicliquids; and mixtures and combinations thereof.

In some embodiments, the disclosed composition includes at least oneionic liquid stabilizer selected from the group consisting of organicsalts that are liquid at room temperature (approximately 25° C.), thosesalts containing cations selected from the group consisting ofpyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium,pyrazolium, thiazolium, oxazolium and triazolium and mixtures thereof;and anions selected from the group consisting of [BF₄]—, [PF₆]—,[SbF₆]—, [CF₃SO₃]—, [HCF₂CF₂SO₃]—, [CF₃HFCCF₂SO₃]—, [HCCIFCF₂SO₃]—,[(CF₃SO₂)₂N]—, [(CF₃CF₂SO₂)₂N]—, [(CF₃SO₂)₃C]—, [CF₃CO₂]—, and F— andmixtures thereof. In some embodiments, ionic liquid stabilizers areselected from the group consisting of emim BF₄(1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF₄(1-butyl-3-methylimidazolium tetraborate); emim PF₆(1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF₆(1-butyl-3-methylimidazolium hexafluorophosphate), all of which areavailable from Fluka (Sigma-Aldrich).

In some embodiments, at least one stabilizer is a hindered phenol, whichare any substituted phenol compound including phenols comprising one ormore substituted or cyclic, straight chain, or branched aliphaticsubstituent group, such as, alkylated monophenols including2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinoneand alkylated hydroquinones including t-butyl hydroquinone, otherderivatives of hydroquinone; and the like, hydroxylated thiodiphenylethers, including 4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tertbutylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); butylatedhydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol), bisphenolscomprising heteroatoms including2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and mixtures andcombinations thereof.

In some embodiments, the disclosed compositions contain at least onetracer. In some embodiments, the tracer additive in the disclosedcompositions consists of two or more tracer compounds from the sameclass of compounds or from different classes of compounds.

In some embodiments, the tracer component or tracer blend is present inthe compositions at a total concentration of about 50 parts per millionby weight (ppm) to about 1000 ppm. In other embodiments, the tracercompound or tracer blend is present at a total concentration of about 50ppm to about 500 ppm. In other embodiment, the tracer compound or tracerblend is present at a total concentration of about 100 ppm to about 300ppm.

In some embodiments, the disclosed compositions include at least onetracer selected from the group consisting of hydrofluorocarbons (HFCs),deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers,brominated compounds, iodated compounds, alcohols, aldehydes andketones, nitrous oxide and combinations thereof. Some embodiments of thedisclosed compositions include at least one tracer selected from thegroup consisting of fluoroethane, 1,1,-difluoroethane,1,1,1-trifluoroethane, 1,1,1,3,3,3-hexafluoropropane,1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,3,3-pentafluoropropane,1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,6,6,7,7,7-tridecafluoroheptane, iodotrifluoromethane,deuterated hydrocarbons, deuterated hydrofluorocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodated compounds,alcohols, aldehydes, ketones, nitrous oxide (N₂O) and mixtures thereof.In some embodiments, the tracer additive is a tracer blend containingtwo or more hydrofluorocarbons, or one hydrofluorocarbon in combinationwith one or more perfluorocarbons.

In some embodiments, at least one tracer composition is added to thedisclosed compositions in previously determined quantities to allowdetection of any dilution, contamination or other alteration of thecomposition.

In other embodiments, the compositions disclosed herein may furtherinclude a perfluoropolyether. A common characteristic ofperfluoropolyethers is the presence of perfluoroalkyl ether moieties.Perfluoropolyether is synonymous to perfluoropolyalkylether. Othersynonymous terms frequently used include “PFPE”, “PFAE”, “PFPE oil”,“PFPE fluid”, and “PFPAE”. In some embodiments, the perfluoropolyetherhas the formula of CF₃—(CF₂)₂—O—[CF(CF₃)—CF₂—O]j′—R′f, and iscommercially available from DuPont under the trademark Krytox®. In theimmediately preceding formula, j′ is 2-100, inclusive and R′f is CF₂CF₃,a C₃ to C₆ perfluoroalkyl group, or combinations thereof.

Other PFPEs, commercially available from Ausimont of Milan, Italy, andMontedison S.p.A., of Milan, Italy, under the trademarks Fomblin® andGalden®, respectively, and produced by perfluoroolefin photooxidation,can also be used.

PFPE commercially available under the trademark Fomblin®-Y can have theformula of CF₃O(CF₂CF(CF₃)—O—)_(m′)(CF₂—O—)_(n′)—R_(1f). Also suitableis CF₃O[CF₂CF(CF₃)O]_(m′)(CF₂CF₂O)_(o′)(CF₂O)_(n′)—R_(1f). In theformulae R_(1f) is CF₃, C₂F₅, C₃F₇, or combinations of two or morethereof; (m′+n′) is 8-45, inclusive; and m/n is 20-1000, inclusive; o′is 1; (m′+n′+o′) is 8-45, inclusive; m′/n′ is 20-1000, inclusive.

PFPE commercially available under the trademark Fomblin®-Z can have theformula of CF₃O(CF₂CF₂—O—)_(p′)(CF₂—O)_(q′)CF₃ where (p′+q′) is 40-180and p′/q′ is 0.5-2, inclusive.

Another family of PFPE, commercially available under the trademarkDemnum™ from Daikin Industries, Japan, can also be used. It can beproduced by sequential oligomerization and fluorination of2,2,3,3-tetrafluorooxetane, yielding the formula ofF—[(CF₂)₃—O]_(t′)—R_(2f) where R_(2f) is CF₃, C₂F₅, or combinationsthereof and t′ is 2-200, inclusive.

In some embodiments, the PFPE is unfunctionalized. In anunfunctionalized perfluoropolyether, the end group can be branched orstraight chain perfluoroalkyl radical end groups. Examples of suchperfluoropolyethers can have the formula ofC_(r′)F_((2r′+1))-A-C_(r′)F_((2r′+1)) in which each r′ is independently3 to 6; A can be O—(CF(CF₃)CF₂—O)_(w′), O—(CF₂—O)_(x′)(CF₂CF₂—O)_(y′),O—(C₂F₄—O)_(w′), O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′),O—(CF(CF₃)CF₂—O)_(x′)(CF₂—O)_(y′), O—(CF₂CF₂CF₂—O)_(w′),O—(CF(CF₃)CF₂—O)_(x′)(CF₂CF₂—O)_(y′)—(CF₂—O)_(z′), or combinations oftwo or more thereof; preferably A is O—(CF(CF₃)CF₂—O)_(w′),O—(C₂F₄—O)_(w′), O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′), O—(CF₂CF₂CF₂—O)_(w′), orcombinations of two or more thereof; w′ is 4 to 100; x′ and y′ are eachindependently 1 to 100. Specific examples include, but are not limitedto, F(CF(CF₃)—CF₂—O)₉—CF₂CF₃, F(CF(CF₃)—CF₂—O)₉—CF(CF₃)₂, andcombinations thereof. In such PFPEs, up to 30% of the halogen atoms canbe halogens other than fluorine, such as, for example, chlorine atoms.

In other embodiments, the two end groups of the perfluoropolyether,independently, may be functionalized by the same or different groups. Afunctionalized PFPE is a PFPE wherein at least one of the two end groupsof the perfluoropolyether has at least one of its halogen atomssubstituted by a group selected from esters, hydroxyls, amines, amides,cyanos, carboxylic acids, sulfonic acids or combinations thereof.

In some embodiments, representative ester end groups include —COOCH₃,—COOCH₂CH₃, —CF₂COOCH₃, —CF₂COOCH₂CH₃, —CF₂CF₂COOCH₃, —CF₂CF₂COOCH₂CH₃,—CF₂CH₂COOCH₃, —CF₂CF₂CH₂COOCH₃, —CF₂CH₂CH₂COOCH₃, —CF₂CF₂CH₂CH₂COOCH₃.

In some embodiments, representative hydroxyl end groups include —CF₂OH,—CF₂CF₂OH, —CF₂CH₂OH, —CF₂CF₂CH₂OH, —CF₂CH₂CH₂OH, —CF₂CF₂CH₂CH₂OH.

In some embodiments, representative amine end groups include —CF₂NR¹R²,—CF₂CF₂NR¹R², —CF₂CH₂NR¹R², —CF₂CF₂CH₂NR¹R², —CF₂CH₂CH₂NR¹R²,—CF₂CF₂CH₂CH₂NR¹R², wherein R¹ and R² are independently H, CH₃, orCH₂CH₃.

In some embodiments, representative amide end groups include—CF₂C(O)NR¹R², —CF₂CF₂C(O)NR¹R², —CF₂CH₂C(O)NR¹R², —CF₂CF₂CH₂C(O)NR¹R²,—CF₂CH₂CH₂C(O)NR¹R², —CF₂CF₂CH₂CH₂C(O)NR¹R², wherein R¹ and R² areindependently H, CH₃, or CH₂CH₃.

In some embodiments, representative cyano end groups include —CF₂CN,—CF₂CF₂CN, —CF₂CH₂CN, —CF₂CF₂CH₂CN, —CF₂CH₂CH₂CN, and

—CF₂CF₂CH₂CH₂CN.

In some embodiments, representative carboxylic acid end groups include—CF₂COOH, —CF₂CF₂COOH, —CF₂CH₂COOH, —CF₂CF₂CH₂COOH, —CF₂CH₂CH₂COOH,—CF₂CF₂CH₂CH₂COOH.

In some embodiments, the sulfonic acid end groups is selected from thegroup consisting of —S(O)(O)OR³, —S(O)(O)R⁴, —CF₂OS(O)(O)OR³,—CF₂CF₂OS(O)(O)OR³, —CF₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂OS(O)(O)OR³,—CF₂CH₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂CH₂OS(O)(O)OR³, —CF₂S(O)(O)OR³,—CF₂CF₂S(O)(O)OR³, —CF₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂S(O)(O)OR³,—CF₂CH₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂CH₂S(O)(O)OR³, —CF₂OS(O)(O)R⁴,—CF₂CF₂OS(O)(O)R⁴, —CF₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂OS(O)(O)R⁴,—CF₂CH₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂CH₂OS(O)(O)R⁴, wherein R³ is H, CH₃,CH₂CH₃, CH₂CF₃, CF₃, or CF₂CF₃, R⁴ is CH₃, CH₂CH₃, CH₂CF₃, CF₃, orCF₂CF₃.

In some embodiments, the disclosed compositions include additives thatare members of the triaryl phosphate family of EP (extreme pressure)lubricity additives, such as butylated triphenyl phosphates (BTPP), orother alkylated triaryl phosphate esters, e.g. Syn-O-Ad® 8478 from AkzoChemicals, tricresyl phosphates and related compounds. Additionally, themetal dialkyl dithiophosphates (e.g., zinc dialkyl dithiophosphate (orZDDP), including the commercially available Lubrizol 1375 and othermembers of this family of chemicals is used in compositions of thedisclosed compositions. Other antiwear additives include natural productoils and asymmetrical polyhydroxyl lubrication additives, such as thecommercially available Synergol TMS (International Lubricants).

In some embodiments, stabilizers such as antioxidants, free radicalscavengers, and water scavengers and mixtures thereof are included. Suchadditives in this category can include, but are not limited to,butylated hydroxy toluene (BHT), epoxides, and mixtures thereof.Corrosion inhibitors include dodecyl succinic acid (DDSA), aminephosphate (AP), oleoyl sarcosine, imidazone derivatives and substitutedsulfphonates.

In one embodiment, the compositions disclosed herein may be prepared byany convenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

In another embodiment, the compositions disclosed herein may be preparedby a method comprising (i) reclaiming a volume of one or more componentsof a refrigerant composition from at least one refrigerant container,(ii) removing impurities sufficiently to enable reuse of said one ormore of the reclaimed components, (iii) and optionally, combining all orpart of said reclaimed volume of components with at least one additionalrefrigerant composition or component.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus, air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates including but not limited tometal, metal salt or elastomer particles, that may have come out of therefrigeration apparatus, air-conditioning apparatus or heat pumpapparatus, and any other contaminants that may adversely effect theperformance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyeffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has three components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

Compositions of the present invention have zero ozone depletionpotential and low global warming potential (GWP). Additionally, thecompositions of the present invention will have global warmingpotentials that are less than many hydrofluorocarbon refrigerantscurrently in use. One aspect of the present invention is to provide arefrigerant with a global warming potential of less than 1000, less than500, less than 150, less than 100, or less than 50.

Methods of Use

The compositions disclosed herein are useful as heat transfercompositions, aerosol propellants, foaming agents, blowing agents,solvents, cleaning agents, carrier fluids, displacement drying agents,buffing abrasion agents, polymerization media, expansion agents forpolyolefins and polyurethane, gaseous dielectrics, fire extinguishingagents, and fire suppression agents. Additionally, in liquid or gaseousform, the disclosed compositions may act as working fluids used to carryheat from a heat source to a heat sink. Such heat transfer compositionsmay also be useful as refrigerants in a cycle wherein the fluidundergoes phase changes; that is, from a liquid to a gas and back orvice versa.

The compositions disclosed herein may be useful as low GWP (globalwarming potential) replacements for currently used refrigerants,including but not limited to R134a (or HFC-134a,1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane),R404A, (ASHRAE designation for a blend of 44 weight percent R125, 52weight percent R143a (1,1,1-trifluoroethane), and 4.0 weight percentR134a), R407A, R407B, R407C, R407D, and R407E (ASHRAE designations forblends of R134a, R125 (pentafluoroethane), and R32 (difluoromethane) indiffering component concentrations), R408A (ASHRAE designation for ablend of 7 weight percent R125, 46 weight percent R143a, and 47 weightpercent R22); R410A (ASHRAE designation for a blend of 50 weight percentR125 and 50 weight percent R32), R413A (ASHRAE designation for a blendcontaining R218, R134a, and isobutane); R417A, (ASHRAE designation for ablend of 46.6 weight percent R125, 50.0 weight percent R134a, and 3.4weight percent n-butane), R419A (ASHRAE designation for a blendcontaining R125, R134a and DME); R422A, R422B, R422C and R422D, (ASHRAEdesignation for blends of R125, R134a, isobutane in differing componentconcentrations), R423A (ASHRAE designation for a blend containing R134aand 1,1,1,2,3,3,3-heptafluoropropane (R227ea)); R424A (ASHRAEdesignation for a blend containing R125, R134a, isobutane, n-butane, andisopentane); R426A (ASHRAE designation for a blend containing R125,R134a, n-butane, and isopentane); R427A (ASHRAE designation for a blendof 15 weight percent R32, 25 weight percent R125, 50 weight percentR134a, and 10 weight percent R143a); R428A (ASHRAE designation for ablend containing R125, R143a, propane and isobutane); R430A (ASHRAEdesignation for a blend containing R152a and isobutane); R434A (ASHRAEdesignation for a blend containing R125, R134a, R143a, and isobutane);R437A (ASHRAE designation for a blend containing R125, R134a, n-butane,and n-pentane); R438A (ASHRAE designation for a blend containing R32,R125, R134a, n-butane, and isopentane); R507A and R507B (ASHRAEdesignation for a blend of R125 and R143a in differing componentconcentrations); and R508A and R508B (ASHRAE designations for blends oftrifluoromethane (R23) and hexafluoroethane (R116) in differingcomponent concentrations).

Additionally, the compositions disclosed herein may be useful asreplacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAEdesignation for a blend of 51.2 weight percent CFC-115(chloropentafluoroethane) and 48.8 weight percent HCFC-22).

Often replacement refrigerants are most useful if capable of being usedin the original refrigeration equipment designed for a differentrefrigerant. In particular, the compositions as disclosed herein may beuseful as replacements for R12, R134a, R22, R404A, R407A, R407C, R408A,R410A, R413A, R417A, R419A, R422A, R422B, R422C, R422D, R423A, R424A.R426A, R428A, R430A, R434A, R437A, R438A, R502, R507A, R507B, and R508,among others in original equipment. Additionally, the compositions asdisclosed herein may be useful as replacements for R12, R134a, R22,R404A, R407A, R407C, R408A, R410A, R413A, R417A, R419A, R422A, R422B,R422C, R422D, R423A, R424A. R426A, R428A, R430A, R434A, R437A, R438A,R502, R507A, R507B, and R508, among others, in equipment designed forthese refrigerants with some system modifications. Further, thecompositions as disclosed herein may be useful for replacing any of theabove mentioned refrigerants in equipment specifically modified for orproduced entirely for these new compositions.

In many applications, some embodiments of the disclosed compositions areuseful as refrigerants and provide at least comparable coolingperformance (meaning cooling capacity and energy efficiency) as therefrigerant for which a replacement is being sought.

In some embodiments, the compositions disclosed herein are useful forany positive displacement compressor system designed for any number ofheat transfer compositions. Additionally, many of the compositionsdisclosed are useful in new equipment utilizing positive displacementcompressors to provide similar performance to the aforementionedrefrigerants.

In one embodiment, disclosed herein is a process to produce coolingcomprising condensing a composition as disclosed herein and thereafterevaporating said composition in the vicinity of a body to be cooled.

In another embodiment, disclosed herein is a process to produce heatcomprising condensing a composition as disclosed herein in the vicinityof a body to be heated and thereafter evaporating said composition.

In some embodiments, the use of the above disclosed compositionsincludes using the composition as a heat transfer composition in aprocess for producing cooling, wherein the composition is first cooledand stored under pressure and when exposed to a warmer environment, thecomposition absorbs some of the ambient heat, expands, and the warmerenvironment is thusly cooled.

In some embodiments, the compositions as disclosed herein may be usefulin particular in air conditioning applications including but not limitedto chillers, high temperature heat pumps, residential, commercial orindustrial air conditioning systems (including residential heat pumps),and including window, ductless, ducted, packaged terminal, chillers, andthose exterior but connected to the building such as rooftop systems.

In some embodiments, the compositions as disclosed herein may be usefulin particular in refrigeration applications including high, medium orlow temperature refrigeration and other specific uses such as incommercial, industrial or residential refrigerators and freezers, icemachines, self-contained coolers and freezers, supermarket rack anddistributed systems, flooded evaporator chillers, direct expansionchillers, walk-in and reach-in coolers and freezers, and combinationsystems.

Additionally, in some embodiments, the disclosed compositions mayfunction as primary refrigerants in secondary loop systems that providecooling to remote locations by use of a secondary heat transfer fluid.

In another embodiment is provided a method for recharging a heattransfer system that contains a refrigerant to be replaced and alubricant, said method comprising removing the refrigerant to bereplaced from the heat transfer system while retaining a substantialportion of the lubricant in said system and introducing one of thecompositions herein disclosed to the heat transfer system.

In another embodiment, a heat exchange system comprising a compositiondisclosed herein is provided, wherein said system is selected from thegroup consisting of air conditioners, freezers, refrigerators, waterchillers, flooded evaporator chillers, direct expansion chillers,walk-in coolers, heat pumps, mobile refrigerators, mobile airconditioning units, and systems having combinations thereof.

In another embodiment is provided a method for replacing a high GWPrefrigerant in a refrigeration, air-conditioning, or heat pumpapparatus, wherein said high GWP refrigerant is selected from the groupconsisting of R134a, R22, R12, R404A, R410A, R407A, R407C, R413A, R417A,R422A, R422B, R422C and R422D, R423A, R427A, R507A, R507B, R502, andR437A, said method comprising providing a composition as disclosedherein to said refrigeration, air-conditioning, or heat pump apparatusthat uses, used or is designed to use said high GWP refrigerant; whereinsaid composition is selected from the group consisting of:

HFO-1234yf and HFC-32;

HFO-1234yf and HFC-134a;

HFO-1234yf, HFC-152a, and HFC-134a;

HFO-1234yf, HFC-125, and HFC-152a;

HFO-1234yf, HFC-125, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-125;

HFO-1234yf, HFC-32, HFC-125, and HFC-134a;

HFO-1234ze and HFC-32;

HFO-1234ze and HFC-125;

HFO-1234ze, HFC-125, and HFC-152a;

HFO-1234ze, HFC-125, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-125; and

HFO-1234ze, HFC-32, HFC-125, and HFC-134a.

In another embodiment, the method for replacing a high GWP refrigerantmay further comprise providing a composition to said refrigeration,air-conditioning, or heat pump apparatus that uses, used or is designedto use said high GWP refrigerant, wherein the composition is selectedfrom the group consisting of:

HFO-1234yf and HFC-32;

HFO-1234yf and HFC-134a;

HFO-1234yf, HFC-152a, and HFC-134a;

HFO-1234yf, HFC-125, and HFC-152a;

HFO-1234yf, HFC-125, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-134a;

HFO-1234yf, HFC-32, and HFC-125;

HFO-1234yf, HFC-32, HFC-125, and HFC-134a;

HFO-1234ze and HFC-32;

HFO-1234ze and HFC-125;

HFO-1234ze, HFC-125, and HFC-152a;

HFO-1234ze, HFC-125, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-134a;

HFO-1234ze, HFC-32, and HFC-125; and

HFO-1234ze, HFC-32, HFC-125, and HFC-134a.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator, by withdrawing heat from theenvironment, at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

In one embodiment, there is provided a heat transfer system containing acomposition as disclosed herein. In another embodiment is disclosed arefrigeration, air-conditioning, or heat pump apparatus containing acomposition as disclosed herein. In another embodiment, is disclosed astationary refrigeration, air-conditioning, or heat pump apparatuscontaining a composition as disclosed herein. In yet another embodimentis disclosed a mobile refrigeration or air conditioning apparatuscontaining a composition as disclosed herein.

In another embodiment, disclosed is a method of using the composition ofthe present invention as a heat transfer fluid composition. The methodcomprises transporting said composition from a heat source to a heatsink.

EXAMPLES

The concepts disclosed herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

Impact of Vapor Leakage

A vessel is charged with an initial composition at a temperature ofabout 23° C., and the initial vapor pressure of the composition ismeasured. The composition is allowed to leak from the vessel, while thetemperature is held constant, until 50 weight percent of the initialcomposition is removed, at which time the vapor pressure of thecomposition remaining in the vessel is measured. Results are shown inTable 2.

TABLE 2 After 50% After 50% Initial P Initial P Leak Leak Delta PComposition wt % (Psia) (kPa) (Psia) (kPa) (%) 1234yf/152a/134a 40/40/2091.0 627 90.5 624 0.5% 20/40/40 88.3 609 87.6 604 0.8% 40/20/40 93.1 64292.7 639 0.4% 98/1/1 93.5 645 93.5 645 0.0% 1/98/1 81.6 563 81.6 5630.0% 1/1/98 90.8 626 90.7 625 0.1% 80/10/10 95.0 655 95.0 655 0.0%10/80/10 84.1 580 83.6 576 0.6% 10/10/80 90.6 625 90.2 622 0.4% 60/20/2094.3 650 94.2 649 0.1% 20/60/20 86.9 599 86.1 594 0.9% 20/20/60 90.6 62590.1 621 0.6% 45/45/10 91.2 629 90.7 625 0.5% 10/45/45 86.1 594 85.5 5900.7% 45/10/45 94.9 654 94.7 653 0.2% 40/30/30 91.9 634 91.4 630 0.5%30/40/30 89.8 619 89.1 614 0.8% 30/30/40 90.8 626 90.2 622 0.7% 86/4/1095.1 656 95.0 655 0.1% 86/5/9 95.1 656 95.0 655 0.1% 65/5/30 96.2 66396.2 663 0.0% 65/30/5 93.6 645 93.4 644 0.2% 5/65/30 84.0 579 83.6 5760.5% 5/30/65 86.6 597 86.2 594 0.5% 30/5/65 94.5 652 94.2 649 0.3%30/65/5 88.2 608 87.5 603 0.8% 90/5/5 94.5 652 94.5 652 0.0% 70/5/2596.1 663 96.1 663 0.0% 1234yf/152a/125 40/40/20 103.4 713 99.0 683 4.3%20/40/40 114.6 790 106.6 735 7.0% 40/20/40 121.8 840 114.4 789 6.1%98/1/1 94.2 649 93.8 647 0.4% 1/98/1 82.1 566 81.8 564 0.4% 1/1/98 186.31285 185.1 1276 0.6% 80/10/10 101.8 702 99.0 683 2.8% 10/80/10 89.3 61686.6 597 3.0% 10/10/80 159.8 1102 152.2 1049 4.8% 60/20/20 107.7 743103.3 712 4.1% 20/60/20 98.4 678 93.6 645 4.9% 20/20/60 136.6 942 127.4878 6.7% 45/45/10 97.1 669 94.6 652 2.6% 10/45/45 115.5 796 106.5 7347.8% 45/10/45 129.6 894 121.5 838 6.3% 40/30/30 111.8 771 105.8 729 5.4%30/40/30 108.9 751 102.7 708 5.7% 30/30/40 118.2 815 110.6 763 6.4%86/4/10 102.0 703 98.9 682 3.0% 86/5/9 101.1 697 98.4 678 2.7% 65/5/30118.7 818 111.7 770 5.9% 65/30/5 96.6 666 95.4 658 1.2% 5/65/30 101.2698 94.3 650 6.8% 5/30/65 134.8 929 124.2 856 7.9% 30/5/65 149.7 1032141.6 976 5.4% 30/65/5 90.9 627 89.2 615 1.9% 90/5/5 97.9 675 96.3 6641.6% 70/5/25 114.5 789 108.2 746 5.5% 1234yf/125/134a 40/40/20 130.0 896122.4 844 5.8% 20/40/40 128.8 888 121.0 834 6.1% 40/20/40 112.9 778107.9 744 4.4% 98/1/1 94.3 650 93.9 647 0.4% 1/98/1 187.3 1291 186.61287 0.4% 1/1/98 91.8 633 91.4 630 0.4% 80/10/10 103.5 714 100.3 6923.1% 10/80/10 167.5 1155 162.1 1118 3.2% 10/10/80 101.2 698 97.7 6743.5% 60/20/20 112.9 778 107.7 743 4.6% 20/60/20 147.7 1018 140.0 9655.2% 20/20/60 111.2 767 105.7 729 4.9% 45/45/10 134.3 926 126.2 870 6.0%10/45/45 132.3 912 123.7 853 6.5% 45/10/45 104.8 723 102.0 703 2.7%40/30/30 121.3 836 114.8 792 5.4% 30/40/30 129.6 894 122.1 842 5.8%30/30/40 120.8 833 114.2 787 5.5% 86/4/10 98.3 678 96.9 668 1.4% 86/5/999.1 683 97.3 671 1.8% 65/5/30 100.9 696 99.4 685 1.5% 65/30/5 120.5 831113.2 780 6.1% 5/65/30 151.1 1042 143.0 986 5.4% 5/30/65 117.8 812 109.9758 6.7% 30/5/65 99.7 687 98.0 676 1.7% 30/65/5 153.1 1056 145.5 10035.0% 90/5/5 98.5 679 96.7 667 1.8% 70/5/25 100.7 694 99.1 683 1.6%35/35/30 125.4 865 118.4 816 5.6% 50/30/20 121.4 837 114.7 791 5.5%45/30/25 121.4 837 114.8 792 5.4% 50/25/25 117.2 808 111.3 767 5.0%45/15/40 108.9 751 104.9 723 3.7% 50/12/38 106.6 735 103.3 712 3.1%1234yf/32/134a 40/40/20 185.3 1278 167.8 1157 9.4% 20/40/40 176.9 1220158.6 1094 10.3% 40/20/40 148.4 1023 128.6 887 13.3% 98/1/1 97.8 67494.7 653 3.2% 1/98/1 231.3 1595 230.9 1592 0.2% 1/1/98 93.5 645 92.1 6351.5% 80/10/10 130.6 900 111.0 765 15.0% 10/80/10 220.2 1518 215.7 14872.0% 10/10/80 117.3 809 105.3 726 10.2% 60/20/20 153.8 1060 131.2 90514.7% 20/60/20 203.9 1406 193.0 1331 5.3% 20/20/60 142.0 979 123.4 85113.1% 45/45/10 195.0 1344 180.0 1241 7.7% 10/45/45 179.5 1238 161.6 111410.0% 45/10/45 126.0 869 111.5 769 11.5% 40/30/30 168.2 1160 148.0 102012.0% 30/40/30 181.2 1249 163.5 1127 9.8% 30/30/40 164.6 1135 144.6 99712.2% 86/4/10 110.7 763 100.6 694 9.1% 86/5/9 114.3 788 102.0 703 10.8%65/5/30 114.0 786 104.0 717 8.8% 65/30/5 176.6 1218 152.9 1054 13.4%5/65/30 202.0 1393 190.1 1311 5.9% 5/30/65 154.1 1062 134.0 924 13.0%30/5/65 109.8 757 102.0 703 7.1% 30/65/5 214.5 1479 207.8 1433 3.1%90/5/5 114.1 787 101.4 699 11.1% 70/5/25 110.4 761 103.8 716 6.0% 90/4/6110.4 761 100.0 689 9.4% 10/40/50 172.3 1188 153.2 1056 11.1% 30/45/25188.7 1301 172.8 1191 8.4% 20/45/35 184.3 1271 167.5 1155 9.1%1234yf/134a/125/32 1/1/1/97 231.2 1594 230.9 1592 0.1% 1/1/97/1 188.81302 187.8 1295 0.5% 1/97/1/1 94.3 650 92.5 638 1.9% 97/1/1/1 98.6 68095.2 656 3.4% 50/38/9/3 113.9 785 106.2 732 6.8% 50/38/8/4 116.1 800107.2 739 7.7% 50/38/7/5 118.4 816 108.2 746 8.6% 20/20/20/40 193.8 1336180.9 1247 6.7% 10/10/10/70 218.2 1504 213.1 1469 2.3% 5/5/5/85 226.21560 224.0 1544 1.0% 5/5/50/40 214.7 1480 210.4 1451 2.0% 50/5/5/40193.4 1333 176.7 1218 8.6% 10/40/10/40 180.7 1246 163.9 1130 9.3%37/50/10/3 113.5 783 106.1 732 6.5% 37/10/50/3 148.2 1022 137.8 950 7.0%50/10/37/3 137.1 945 126.0 869 8.1% 10/50/37/3 132.8 916 122.7 846 7.6%70/20/8/2 110.2 760 103.5 714 6.1% 20/70/8/2 106.6 735 101.0 696 5.3%8/20/70/2 162.0 1117 154.3 1064 4.8% 70/8/20/2 119.4 823 110.1 759 7.8%35/25/30/10 149.2 1029 134.7 929 9.7% 92/1/1/6 118.2 815 102.9 709 12.9%1/92/1/6 106.3 733 98.5 679 7.3% 1/1/92/6 195.5 1348 193.7 1336 0.9%74/10/10/6 125.3 864 110.7 763 11.7% 10/74/10/6 116.4 803 106.1 732 8.8%10/10/74/6 177.0 1220 169.8 1171 4.1% 54/20/20/6 132.6 914 119.0 82010.3% 20/54/20/6 127.3 878 115.7 798 9.1% 20/20/54/6 158.3 1091 147.71018 6.7% 34/30/30/6 138.5 955 126.2 870 8.9% 30/34/30/6 137.9 951 125.7867 8.8% 30/30/34/6 141.4 975 129.3 891 8.6% 40/27/27/6 136.7 943 124.2856 9.1% 27/40/27/6 134.7 929 122.8 847 8.8% 27/27/40/6 146.3 1009 134.5927 8.1% 50/22/22/6 133.6 921 120.5 831 9.8% 22/50/22/6 129.5 893 117.7812 9.1% 22/22/50/6 154.8 1067 143.7 991 7.2% 88/1/1/10 131.7 908 110.2760 16.3% 1/88/1/10 115.2 794 103.6 714 10.1% 1/1/88/10 200.1 1380 198.01365 1.0% 70/10/10/10 137.5 948 118.6 818 13.7% 10/70/10/10 125.8 867112.2 774 10.8% 10/10/70/10 182.3 1257 174.5 1203 4.3% 50/20/20/10 143.2987 127.0 876 11.3% 20/50/20/10 137.1 945 122.9 847 10.4% 20/20/50/10164.5 1134 152.5 1051 7.3% 40/25/25/10 145.7 1005 130.7 901 10.3%25/40/40/10 142.7 984 128.4 885 10.0% 25/25/40/10 156.1 1076 142.8 9858.5% 78/1/1/20 158.6 1094 131.4 906 17.2% 1/78/1/20 135.4 934 117.7 81213.1% 1/1/78/20 209.3 1443 206.9 1427 1.1% 60/10/10/20 161.9 1116 139.8964 13.7% 10/60/10/20 146.7 1011 128.7 887 12.3% 10/10/60/20 193.2 1332184.8 1274 4.3% 40/20/20/20 165.1 1138 147.2 1015 10.8% 20/40/20/40158.9 1096 141.9 978 10.7% 20/20/40/20 177.0 1220 163.5 1127 7.6%30/25/25/20 166.5 1148 150.0 1034 9.9% 25/30/25/20 164.9 1137 148.6 10259.9% 25/25/30/20 169.4 1168 153.9 1061 9.1% 68/1/1/30 178.4 1230 154.01062 13.7% 1/68/1/30 153.1 1056 133.0 917 13.1% 1/1/68/30 215.9 1489213.8 1474 1.0% 50/10/10/30 179.9 1240 160.6 1107 10.7% 10/50/10/30164.9 1137 146.2 1008 11.3% 10/10/50/30 201.3 1388 193.3 1333 4.0%40/15/15/30 180.7 1246 163.4 1127 9.6% 15/40/15/30 171.3 1181 153.8 106010.2% 15/15/40/30 193.7 1336 182.2 1256 5.9% 30/20/20/30 181.4 1251165.6 1142 8.7% 20/30/20/30 177.6 1225 161.5 1114 9.1% 20/20/30/30 186.51286 173.0 1193 7.2% 59/1/1/39 191.9 1323 172.8 1191 10.0% 1/59/1/39167.2 1153 147.4 1016 11.8% 1/1/59/39 220.3 1519 218.6 1507 0.8%40/10/11/39 192.8 1329 177.80 1226 7.8% 10/40/11/39 180.1 1242 163.201125 9.4% 11/10/40/39 206.4 1423 198.70 1370 3.7% 30/15/16/39 193.0 1331179.30 1236 7.1% 15/30/16/39 186.6 1287 171.70 1184 8.0% 16/15/30/39199.4 1375 188.90 1302 5.3%

The compositions as listed in Table 2 are near-azeotropic when thecomposition remaining after 50 weight percent is removed is less thanabout 10 percent.

Example 2

Glide Reduction

The temperature glide and other cooling performance parameters for acomposition containing HFO-1234yf and HFC-32 is determined and displayedin Table 3 as compared to R407C (ASHRAE designation for a refrigerantblend containing 23 wt % HFC-32, 25 wt % HFC 125 and 52 wt % HFC-134a).The glide, pressures, discharge temperatures, COP (energy efficiency)and cooling capacity are determined for the following conditions:

Evaporator temperature 41° F. (5° C.) Condenser temperature 104° F. (40°C.) Subcool amount 41° F. (5° C.) Return gas temperature  59° F. (15°C.) Compressor efficiency is 70%

TABLE 3 Pres Pres Disch evap, cond, Temp, Capacity Glide, ° C.Composition kPa kPa ° C. COP (kJ/m³) (Cond/Evap) R407C 584 1627 71.34.53 3978  5/4.8 HFO-1234yf 371 1016 54.6 4.722 2516 0 HFO-1234yf/HFC-32421 1159 57.5 4.598 2799 3.7/2.6 (95/5 wt %) HFO-1234yf/HFC-32 469 129160.1 4.5 3067 5.8/4.4 (90/10 wt %) HFO-1234yf/HFC-32 515 1412 62.5 4.453325 6.9/5.5 (85/15 wt %) HFO-1234yf/HFC-32 559 1523 64.6 4.416 35757.3/6  (80/20 wt %) HFO-1234yf/HFC-32 572 1556 65.3 4.408 3648 7.3/6.1(78.5/21.5 wt %)R407C is currently a commercial refrigerant product even with the glideas reported in the table above. This data indicate that HFC-32concentrations of 15 weight percent or below more closely approach thetemperature glide for R407C, which is an amount that has been acceptablein certain applications.

Example 3

Flammability

Flammable compounds may be identified by testing under ASTM (AmericanSociety of Testing and Materials) E681-2004, with an electronic ignitionsource. Such tests of flammability were conducted on compositions of thepresent disclosure at 101 kPa (14.7 psia), 50 percent relative humidity,and 60° C. or 100° C. at various concentrations in air in order todetermine if flammable and if so, find the lower flammability limit(LFL) and the upper flammability limit (UFL). The results are given inTable 4.

TABLE 4 Temperature, ° C. 60° C. 100° C. LFL UFL LFL UFL (vol % in (vol% in (vol % in (vol % in Composition air) air) air) air)HFO-1234yf/HFC-134a non- non- non- non- (50/50 wt %) flammable flammableflammable flammable HFO-1234yf/HFC-134a non- non- non- non- (52.5/47.5wt %) flammable flammable flammable flammable HFO-1234yf/HFC-134a non-non- 10 10 (53.75/46.25 wt %) flammable flammable HFO-1234yf/HFC-134anon- non- 9.0 10.5 (55/45 wt %) flammable flammable HFO-1234yf/HFC-134anon- non- 8.0 12 (57.5/42.5 wt %) flammable flammableHFO-1234yf/HFC-134a non- non- not tested not tested (60/40 wt %)flammable flammable HFO-1234yf/HFC-134a 10 11 not tested not tested(60.6/39.4 wt %) HFO-1234yf/HFC-134a 8.8 10.8 not tested not tested(62.5/37.5 wt %) HFO-1234yf/HFC-134a 8.0 12 not tested not tested (65/35wt %)

The results indicate that compositions comprising no more than about 60weight percent HFO-1234yf and the remainder being HFC-134a arenon-flammable at 60° C. Additionally, compositions comprising no morethan about 53 weight percent HFC-1234yf and the remainder being HFC-134aare non-flammable at 100° C. Those compositions comprising fluoroolefinsthat are non-flammable are more acceptable candidates as refrigerant orheat transfer fluid compositions.

Example 4

Global Warming Potentials

Values for global warming potential (GWP) for some of the disclosedcompositions are listed in Table 5 as compared to GWP values forHCFC-22, HFC-134a, R404A, R407C, R410A and other currently usedrefrigerants. The GWP for the pure components are listed for reference.The GWP values for compositions containing more than one component arecalculated as weighted averages of the individual component GWP values.The values for the HFCs are taken from the “Climate Change 2007—IPCC(Intergovernmental Panel on Climate Change) Fourth Assessment Report onClimate Change”, from the section entitled “Working Group 1 Report: “ThePhysical Science Basis”, Chapter 2, pp. 212-213, Table 2.14. The valuefor HFO-1234yf was published in Papadimitriou et al., Physical ChemistryChemical Physics, 2007, vol. 9, pp. 1-13. Specifically, the 100 yeartime horizon GWP values are used.

TABLE 5 Component or composition GWP HCFC-22 1810 HFC-134a 1430 HFC-152a124 HFC-125 3500 HFC-32 675 HFC-143a 4470 HFO-1234ze 6 HFO-1234yf 4R404A 3922 R407C 1802 R410A 2088 HFO-1234yf/HFC-134a (60/40 wt %) 860HFO-1234yf/HFC-134a (50/50 wt %) 717 HFO-1234yf/HFC-32 (78.5/21.5 wt %)148 HFO-1234yf/HFC-32 (85/15 wt %) 105 HFO-1234yf/HFC-32 (90/10 wt %) 71HFO-1234yf/HFC-32/HFC-125/HFC-134a (35/10/30/25 wt %) 1476HFO-1234yf/HFC-32/HFC-125/HFC-134a (97/1/1/1 wt %) 57HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/97/1/1 wt %) 704HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/1/97/1 wt %) 3415HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/1/1/97 wt %) 1490HFO-1234yf/HFC-32/HFC-125/HFC-134a (92/5/1/1 wt %) 87HFO-1234yf/HFC-32/HFC-125/HFC-134a (50/40/5/5 wt %) 519HFO-1234yf/HFC-32/HFC-125/HFC-134a (34/6/30/30 wt %) 1520HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/20/78/1 wt %) 2879HFO-1234yf/HFC-32/HFC-125/HFC-134a (74/6/10/10 wt %) 254HFO-1234yf/HFC-32/HFC-125/HFC-134a (27/6/27/40 wt %) 1559HFO-1234yf/HFC-32/HFC-125 (40/10/50 wt %) 1819 HFO-1234yf/HFC-32/HFC-125(8/50/42 wt %) 1808 HFO-1234yf/HFC-32/HFC-125 (60/30/10 wt %) 555HFO-1234yf/HFC-32/HFC-125 (20/20/60 wt %) 2236 HFO-1234yf/HFC-32/HFC-125(44/20/36 wt %) 1397 HFO-1234yf/HFC-32/HFC-125 (70/15/15 wt %) 629HFO-1234yf/HFC-32/HFC-125 (70/20/10 wt %) 488 HFO-1234yf/HFC-32/HFC-125(60/10/30 wt %) 1120 HFO-1234yf/HFC-32/HFC-134a (1/1/98 wt %) 1409HFO-1234yf/HFC-32/HFC-134a (1/4/95 wt %) 1386 HFO-1234yf/HFC-32/HFC-134a(95/4/1 wt %) 45 HFO-1234yf/HFC-32/HFC-134a (1/98/1 wt %) 676HFO-1234yf/HFC-32/HFC-134a (98/1/1 wt %) 25 HFO-1234yf/HFC-32/HFC-134a(54/45/1 wt %) 320 HFO-1234yf/HFC-32/HFC-134a (1/45/54 wt %) 1076HFO-1234yf/HFC-32/HFC-134a (45/45/10 wt %) 320HFO-1234yf/HFC-32/HFC-134a (30/45/25 wt %) 662HFO-1234yf/HFC-32/HFC-134a (30/65/5 wt %) 511HFO-1234yf/HFC-152a/HFC-134a (1/1/98 wt %) 1401HFO-1234yf/HFC-152a/HFC-134a (1/98/1 wt %) 136HFO-1234yf/HFC-152a/HFC-134a (98/1/1 wt %) 19HFO-1234yf/HFC-125/HFC-152a (1/1/98 wt %) 157HFO-1234yf/HFC-125/HFC-152a (98/1/1 wt %) 40 HFO-1234yf/HFC-125/HFC-152a(1/98/1 wt %) 3431 HFO-1234yf/HFC-125/HFC-134a (1/1/98 wt %) 1436HFO-1234yf/HFC-125/HFC-134a (1/98/1 wt %) 3444HFO-1234yf/HFC-125/HFC-134a (98/1/1 wt %) 53 HFO-1234ze/HFC-134a (50/50wt %) 718 HFO-1234ze/HFC-134a (80/20 wt %) 293 HFO-1234ze/HFC-125 (95/5wt %) 184 HFO-1234ze/HFC-125 (80/20 wt %) 705 HFO-1234ze/HFC-32 (30/70wt %) 474 HFO-1234ze/HFC-32 (60/40 wt %) 274 HFO-1234ze/HFC-32 (80/20 wt%) 140

Many compositions as disclosed herein, such as those listed in Table 5,provide lower GWP alternatives to HCFC-22, HFC-134a, R404A, R407C,and/or R410A etc.

Example 5

Cooling Performance

Table 6 shows the performance of some exemplary compositions as comparedto HCFC-22, HFC-134a, HFO-1234yf, R410A, and R407C. In Table 6, EvapPres is evaporator pressure, Cond Pres is condenser pressure, Comp DischT is compressor discharge temperature, COP is coefficient of performance(analogous to energy efficiency), and CAP is capacity. The data arebased on the following conditions.

Evaporator temperature  45° F. (7.2° C.) Condenser temperature 110° F.(43.3° C.) Subcool amount  2.8° F. (5° C.) Return gas temperature  65°F. (18° C.) Compressor efficiency is 70%

Note that the evaporator superheat enthalpy is included in coolingcapacity and energy efficiency determinations.

TABLE 6 Evap Cond Compr CAP relative COP relative Temp Press Press DischTemp CAP to R407C to R407C Glide, ° C. Composition (kPa) (kPa) (° C.)(kJ/m³) (%) COP (%) (cond/evap) R22 624 1660 85 4112 99.1 4.49 103 0HFC-134a 377 1110 67 2709 65.3 4.58 105 0 HFO-1234yf 399 1104 59 256461.8 4.44 102 0 R410A 991 2589 83 5830 141 4.12 94.7 0.14/0.14 R407C6.25 1767 76 4151 100 4.36 100 4.8/4.8 HFO-1234yf/HFC-134a 411 1164 622763 66.6 4.50 103   0.01 (60/40 wt %) HFO-1234yf/HFC-32 6101 1685 703835 92.4 4.29 98.4 7.1/6.1 (78.5/21.5 wt %) HFO-1234yf/HFC-32 578 160368 3654 88.0 4.31 98.9  7/5.8 (82/18 wt %) HFO-1234yf/HFC-32 549 1529 673493 84.1 4.32 99.3 6.8/5.4 (85/15 wt %) HFO-1234yf/HFC- 590 1638 673738 90.0 4.32 99.1 4.1/3.6 32/HFC-125/HFC-134a (35/10/30/25 wt %)

Several described compositions have capacity greater than the capacityof HFC-134a, HFO-1234yf and within 10% of the capacity of R407C. Energyefficiency (as displayed as COP), is within 2% of the efficiency forR407C.

Example 6

Heating Performance

Table 7 shows the performance of some exemplary compositions as comparedto HCFC-22, HFC-134a, HFO-1234yf, and R410A. In Table 7, Evap Pres isevaporator pressure, Cond Pres is condenser pressure, Comp Disch T iscompressor discharge temperature, COP is coefficient of performance(analogous to energy efficiency), and CAP is capacity. The data arebased on the following conditions.

Condenser temperature 20° F. (−6.7° C.) Evaporator temperature 80° F.(26.7° C.) Subcool amount 10° F. (5.6° C.) Return gas temperature 65° F.(18° C.) Compressor efficiency is 70%

TABLE 7 Cond Evap Compr CAP relative COP relative Temp Press Press DischTemp CAP to HCFC-22 to HCFC-22 Glide, ° C. Composition (kPa) (kPa) (°C.) (kJ/m3) (%) COP (%) (cond/evap) R22 397 1091 85 2948 100 4.85 100 0HFC-134a 228 699 67 1897 64.3 5.02 104 0 HFO-1234yf 249 713 58 1914 64.95.03 104 0 R410A 393 1145 75 2965 101 4.74 97.8 0.55/0.52HFO-1234yf/HFC-134a 251 744 63 2009 68.1 5.03 104  0/0.1 (50/50 wt %)HFO-1234yf/HFC-32 392 1109 69 2812 95.4 4.70 96.9 7.9/6.7 (78.5/21.5 wt%) HFO-1234yf/HFC- 374 1069 66 2757 93.5 4.80 98.9 4.6/4.132/HFC-125/HFC-134a (35/10/30/25 wt %)

Several described compositions have capacity within 7% of the capacityof HCFC-22. Energy efficiency (as displayed as COP) for thesecompositions is better than or within 4% of the efficiency for HCFC-22.

Example 7

Heating Performance

Table 8 shows the performance of some exemplary compositions as comparedto HCFC-22, and HFO-1234yf/HFC-32 compositions. In Table 8, Evap Pres isevaporator pressure, Cond Pres is condenser pressure, Comp Disch T iscompressor discharge temperature, COP is coefficient of performance(analogous to energy efficiency), and CAP is capacity. The data arebased on the following conditions.

Evaporator temperature 32° C. Condenser temperature −12° C.  Subcoolamount  9° C. Return gas temperature −9° C. Compressor efficiency is 70%

TABLE 8 Cond Evap Compr Cond/Evap 100 yr GWP Pressure Pressure Exit TempAvg Temp Glide Capacity COP Rel Cap Rel (IPCC AR4) (kPa) (kPa) (° C.) (°C.) COP (kJ/m{circumflex over ( )}3) to R-22 to R-22 HCFC-22 1810 3301254 76.9 0 4.598 3133.4 100%  103%  HFO-1234yf 4 205 824 42.7 0 4.5331876.1 99% 62% HFO-1234yf/HFC-32 105 290 1155 52.3 6.6 4.521 2657.0 98%88% (85/15 wt %) HFO-1234yf/HFC-32 111 295 1174 52.9 6.7 4.520 2703.798% 89% (84/16 wt %) HFO-1234yf/HFC-32 125 305 1211 54.0 6.9 4.5172795.4 98% 92% (82/18 wt %) HFO-1234yf/HFC-32 138 316 1247 55.1 7.14.513 2885.1 98% 95% (80/20 wt %) HFO-1234yf/HFC-32 145 321 1265 55.67.1 4.512 2929.1 98% 97% (79/21 wt %)

In heating mode, compositions of HFO-1234yf from 79-85 wt % and HFC-32from 15-21 wt % have equivalent energy efficiency to R-22 and capacityfrom 88-97% of R-22. These compositions also have 100 year GWP less than150 indicating they would be an excellent low GWP replacement for R-22in heat pumps.

Example 8 Cooling Performance

Table 9 shows the performance of some exemplary compositions as comparedto HFC-134a. In Table 9, Evap Pres is evaporator pressure, Cond Pres iscondenser pressure, Comp Disch T is compressor discharge temperature,COP is coefficient of performance (analogous to energy efficiency), CAPis cooling capacity, Avg. Temp. glide is the average of the temperatureglide in the evaporator and condenser, and GWP is global warmingpotential. The data are based on the following conditions.

Evaporator temperature −10° C.   Condenser temperature 40.0° C.  Subcool amount  6° C. Return gas temperature 10° C. Compressorefficiency is 70%

Note that the evaporator superheat enthalpy is not included in coolingcapacity and energy efficiency determinations.

TABLE 9 Evap Cond Compr CAP relative COP relative Press Press Disch TempCAP to 134a to 134a Avg. Temp. Composition (kPa) (kPa) (° C.) (kW) (%)COP (%) Glide, ° C. GWP* HFC-134a 200.6 1016.5 81.4 2.231 2.742 0 1430HFO-1234yf 220.5 1015.6 68.3 2.113 94.7 2.580 94.1 0 4HFO-1234ze/HFC-125 156.7 814.4 76.3 1.769 79 2.756 101 1.61 184 (95/5 wt%) HFO-1234ze/HFC-125 166.6 864.4 76.4 1.869 84 2.746 100 2.96 355(90/10 wt %) HFO-1234ze/HFC-125 176.9 915.0 76.4 1.968 88 2.735 100 4.08530 (85/15 wt %) HFO-1234ze/HFC-125 187.7 966.1 76.4 2.067 93 2.718 994.99 705 (80/20 wt %) *The GWP value for HFC-134a is taken from the“Climate Change 2007 - IPCC (Intergovernmental Panel on Climate Change)Fourth Assessment Report on Climate Change”, from the section entitled“Working Group 1 Report: “The Physical Science Basis”, Chapter 2, pp.212-213, Table 2.14. The value for HFO-1234yf was published inPapadimitriou et al., Physical Chemistry Chemical Physics, 2007, vol. 9,pp. 1-13. Specifically, the 100 year time horizon GWP values are used.The GWP values for the compositions containing HFC-134a and HFO-1234yfare calculated as weighted averages of the individual component GWPvalues.

The data in Table 9 indicates that the HFO-1234ze/HFC-125 compositionscould serve as a replacement for HFC-134a, having performance similar toHFC-134a. In particular, these compositions provide matching energyefficiency (shown as COP), pressures and temperatures in the system,with lower GWP values, and only a minor reduction in cooling capacity.Plus, all the compositions have relatively low temperature glide and aspecific composition could be selected based on regulatory requirementsfor GWP, which have not at this time been determined.

Example 9 Cooling Performance

Table 10 shows the performance of certain compositions as compared toCO₂, R404A (ASHRAE designation for a mixture containing HFC-125,HFC-134a, and HFC-143a), R410A (ASHRAE designation for a mixturecontaining HFC-32 and HFC-125) and HFC-32. In Table 10, Evap Pres isevaporator pressure, Cond Pres is condenser pressure, Comp Disch T iscompressor discharge temperature, COP is coefficient of performance(analogous to energy efficiency), CAP is capacity, Avg. Temp. glide isthe average of the temperature glide in the evaporator and condenser,and GWP is global warming potential. The data are based on the followingconditions.

Evaporator temperature −35° C. Condenser temperature  −6° C. Subcoolamount    0° C. Return gas temperature −25° C. Compressor efficiency is70%

Note that the evaporator superheat enthalpy is not included in coolingcapacity and energy efficiency determinations.

TABLE 10 Evap Cond Compr Press Press Disch Temp CAP Avg. Temp.Composition (kPa) (kPa) (° C.) (kW) COP Glide, ° C. GWP* CO₂ 1204.72960.8 57.3 12.132 4.229 0 1 R404A 168.3 449.4 20.0 2.175 4.791 0.5 3922HFO-1234yf/HFC-32 163.6 503.5 31.5 2.271 4.875 6.7 252 (63/37 wt %)R410A 220.1 654.1 38.3 2.966 4.836 0.1 2088 HFO-1234yf/HFC-32 213.6635.4 46.4 2.934 4.865 0.8 490 (27.5/72.5 wt %) HFO-1234yf/HFC-32 185.6561.8 36.9 2.547 4.853 4.3 340 (50/50 wt %) HFO-1234yf/HFC-32 200.2599.6 41.0 2.739 4.851 2.5 407 (40/60 wt %) HFO-1234yf/HFC-32 218.2649.8 50.2 3.015 4.852 0.3 541 (20/80 wt %) HFC-32 221.0 666.3 60.83.126 4.833 0 675 HFO-1234ze/HFC-32 60.8 220.1 28.6 0.982 4.947 4.7 73(90/10 wt %) HFO-1234ze/HFC-32 74.7 266.2 33.2 1.201 4.958 7.5 140(80/20 wt %) HFO-1234ze/HFC-32 89.1 311.4 37.4 1.419 4.968 9.1 207(70/30 wt %) HFO-1234ze/HFC-32 104.1 356.1 41.4 1.637 4.958 9.8 274(60/40 wt %) HFO-1234ze/HFC-32 119.6 400.9 45.2 1.855 4.944 9.8 341(50/50 wt %) HFO-1234ze/HFC-32 135.9 446.6 48.8 2.074 4.927 9.2 407(40/60 wt %) HFO-1234ze/HFC-32 144.1 469.9 50.6 2.185 4.907 8.6 441(35/65 wt %) HFO-1234ze/HFC-32 153.0 493.8 52.4 2.298 4.892 8.0 474(30/70 wt %) HFO-1234ze/HFC-32 162.1 518.4 54.1 2.413 4.875 7.2 508(25/75 wt %) HFO-1234ze/HFC-32 171.7 543.9 55.7 2.532 4.858 6.2 541(20/80 wt %) HFO-1234ze/HFC-32 193.1 599.4 58.7 2.793 4.830 3.7 608(10/90 wt %) *The GWP value for HFCs are taken from the “Climate Change2007 - IPCC (Intergovernmental Panel on Climate Change) FourthAssessment Report on Climate Change”, from the section entitled “WorkingGroup 1 Report: “The Physical Science Basis”, Chapter 2, pp. 212-213,Table 2.14. The value for HFO-1234yf was published in Papadimitriou etal., Physical Chemistry Chemical Physics, 2007, vol. 9, pp. 1-13.Specifically, the 100 year time horizon GWP values are used. The GWPvalues for the compositions containing more than one component arecalculated as weighted averages of the individual component GWP values.

The composition containing 63 wt % HFO-1234yf and 37 wt % HFC-32actually shows improved COP and capacity relative to R404A and also hassignificantly lower GWP. The composition containing 27.5 wt % HFO-1234yfand 72.5 wt % HFC-32 matches the COP and capacity of R410A, has very lowtemperature glide indicating azeotrope-like behavior and also hassignificantly lower GWP. Note that all mixtures of tetrafluoropropene(both HFO-1234yf and HFO-1234ze) and HFC-32 have improved COP (energyefficiency) as compared to CO₂, and many have improved COP as comparedto R404A and R410A as well.

What is claimed is:
 1. A composition comprising a refrigerant consistingof from about 20 weight percent to about 80 weight percent HFO-1234yf,about 5 weight percent to about 40 weight percent HFC-134a, and about 5weight percent to about 40 weight percent HFC-152a.
 2. The compositionof claim 1, further containing at least one non-refrigerant componentselected from the group consisting of lubricants, dyes, solubilizingagents, compatibilizers, stabilizers, tracers, perfluoropolyethers,anti-wear agents, extreme pressure agents, corrosion and oxidationinhibitors, metal surface energy reducers, metal surface deactivators,free radical scavengers, foam control agents, viscosity index improvers,pour point depressants, detergents, viscosity adjusters, and mixturesthereof.
 3. The composition of claim 2, wherein said lubricant isselected from the group consisting of mineral oils, alkylbenzenes,synthetic paraffins, synthetic naphthenes, poly alpha olefins,polyalkylene glycols, dibasic acid esters, polyol esters, neopentylesters, polyvinyl ethers, silicones, silicate esters, fluorinatedcompounds, phosphate esters and mixtures thereof.
 4. The composition ofclaim 2, wherein said stabilizer is selected from the group consistingof hindered phenols, thiophosphates, butylatedtriphenylphosphorothionates, organophosphates, or phosphites, aryl alkylethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes,ascorbic acid, thiols, lactones, thioethers, amines, nitromethane,alkylsilanes, benzophenone derivatives, aryl sulfides, divinylterephthalic acid, diphenyl terephthalic acid, ionic liquids, andmixtures thereof.
 5. The composition of claim 4, wherein said stabilizeris selected from butylated hydroxytoluene, d-limonene, nitromethane ormixtures thereof.
 6. A process to produce cooling comprising condensinga composition of claim 1 and thereafter evaporating said composition inthe vicinity of a body to be cooled.
 7. A process to produce heatcomprising condensing the composition of claim 1 in the vicinity of abody to be heated and thereafter evaporating said composition.
 8. Amethod for replacing R12, or R134a, in a system that uses, used or wasdesigned to use R12, or R134a, wherein said method comprises providingthe composition of claim 1 to said system.
 9. A refrigeration,air-conditioning or heat pump apparatus containing the composition ofclaim
 1. 10. A stationary air conditioning apparatus containing thecomposition of claim
 1. 11. A stationary refrigeration system containingthe composition of claim 1.